Sciencemadness Discussion Board

2-amino-4,N-methylamino butane

chemrox - 19-1-2007 at 22:16

A few years ago a chemical company sent me a sample of benzyl acetone. Nice smelling stuff. So, just for grins, I'm thinking of hitting it with Hg/Al amalgam and adding ammonia. I don't have CH3NH2 but was planning to make the sec amine with CH3I.

All comments and ideas for the ketone welcome.

one more thing

chemrox - 19-1-2007 at 22:17

As most ot all of you know the TM has zero activity.

Sergei_Eisenstein - 20-1-2007 at 00:06

Controlled alkylation of amines with alkylhalogenides generally is difficult. I'd expect a mixture of mono-, di- and trimethylated amine. Better ideas (regarding selectivity) are reductive amination or reduction of a corresponding amide (e.g. LAH reduction of N-formylamines to N-methylamines). Also, I'm not sure the reductive amination of your ketone with amine can be achieved under normal reaction conditions. Most experiments I have seen involve high pressure.

[Edited on 20-1-2007 by Sergei_Eisenstein]

chemrox - 20-1-2007 at 15:30

I believe you're right as to yield issues in going to the sec amine the way I indicated although there may be a way to control formation of tert ams and quart am salts. I'm looking around for a possible solution to that. Option is to go straight there using the appropriate amine or amide. Might have to.

You're wrong about the reduction requirements though. Shulgin uses Fe/HCl in at least on correspondng synthesis and there are boundless others in the underground anals. I'll report results of that phase when I get to it. Also, before I do it, I'll look up some refs and report those so you have more than, "Shulgin uses..." to critique.

Thanks for your thoughts and information.

Sergei_Eisenstein - 21-1-2007 at 01:03

I made a typo.
Quote:
Also, I'm not sure the reductive amination of your ketone with amine can be achieved under normal reaction conditions


It should read: Also, I'm not sure the reductive amination of your ketone with ammonia can be achieved under normal reaction conditions. I would be interested to see the reports where they use Fe/HCl for reductive aminations. I'm completely unaware of that. I suspect you're confusing a few things with eachother.

Nicodem - 21-1-2007 at 07:00

The amination of phenylacetone with NH3 using aluminium amalgam is described in J. Chem. Educ., 51 (1974) 671 (see this). However the 30% yield achieved is understandably much lower as to the yield when using alkylamines which form the imine intermediate more readily given their considerably greater nucleophilicity. I would expect the same reaction for benzylacetone would give similarly low yields. After all, it is not without any reason that everybody uses oximes in such cases where a primary amine is to be formed from a ketone!
Quote:
Originally posted by chemrox
As most ot all of you know the TM has zero activity.

I have no idea what the hell "TM" is supposed to be, but I would not be so sure regarding the inactivity of the resulting 4-phenyl-2-aminobutane and its N-methyl derivative.
Quote:
Originally posted by chemrox
Shulgin uses Fe/HCl in at least on correspondng synthesis and there are boundless others in the underground anals.

Strange. I never heard of a single such case where Fe/HCl is used in reductive aminations of ketones.


Edit:
Just curious, but what has the thread title "2-amino-4,N-methylamino butane" to do with the thread topic?


[Edited on 21-1-2007 by Nicodem]

chemrox - 24-1-2007 at 15:40

TM=target molecule => title

chemrox - 24-1-2007 at 15:42

Quote:
Originally posted by Nicodem
The amination of phenylacetone with NH3 using aluminium amalgam is described in J. Chem. Educ., 51 (1974) 671 (see this). However the 30% yield achieved is understandably much lower as to the yield when using alkylamines which form the imine intermediate more readily given their considerably greater nucleophilicity. I would expect the same reaction for benzylacetone would give similarly low yields. After all, it is not without any reason that everybody uses oximes in such cases where a primary amine is to be formed from a ketone!

Quote:
Originally posted by chemrox
As most ot all of you know the TM has zero activity.

I have no idea what the hell "TM" is supposed to be, but I would not be so sure regarding the inactivity of the resulting 4-phenyl-2-aminobutane and its N-methyl derivative.
Quote:
Originally posted by chemrox
Shulgin uses Fe/HCl in at least on correspondng synthesis and there are boundless others in the underground anals.

Strange. I never heard of a single such case where Fe/HCl is used in reductive aminations of ketones.


Edit:
Just curious, but what has the thread title "2-amino-4,N-methylamino butane" to do with the thread topic?


[Edited on 21-1-2007 by Nicodem]

chemrox - 24-1-2007 at 15:44

As far as reduction using ammonia, I think I was confusing a couple of things as has been sugested.